Reaction products of tetrahalogenated quinoid compounds and trisecondary alkyl phosphites and process of making same



' 2,935,518] REACTION PRODUCTS'OF TETRAHALOGENATED QUINOID COMPOUNDS AND. TRISECONDARY ALKYL PHOSPHITES AND PROCESS OF MAK- use SAME Theodor Reetz, Webster Groves, Mo., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application September 12, 1958 Serial No. 760,570

9 Claims. or. 260-396) United States Eatent '"ice Later Perkov discovered that the main product of the above reaction is not a phosphonate but a phosphate, thereby establishing that the Arbusov reaction was merely a side reaction as indicated by the fact that only 5-6 percent of the phosphonate was formed. Accordingly a new reaction was discovered which took place as follows:

CH:C|CH:C1+P(OCaHs)r- CH3C=CH;+C:H;C1 P00302110! In the case of chlorinated quinones with which the present application is primarily concerned, the reaction with trialkylphosphites was also considered to be an Arbusov type reaction as follows:

III. 0 0

Cl- C] However, Ramirez published some papers which established that Reaction III above with its formation of a phosphonate was not representative of the principal reaction which occurred but rather the reaction proceeded as follows:

where R is ethyl.

G. M. Kosolapotf, Organophosphorus Compounds," 121, John Wiley, New York (1950).

2 W. Perkov et al. Chem. Ber. 88, 662 (1955).

a. o. Ladd, dA 2,609,376.

F. Ramirez, J. Org. Chem. 22, #865 (1957).

47, 7540 (1953); also US. Patent 2,935,518 Patented May 3, 1960 I have also found that the reaction took place as set forth in Equation IV and in addition have noted that phosphates were also formed when chloranil was reacted with trimethyl phosphite, tri-n-propyl phosphite, tri-n-butyl phosphite, tri-ethylhexyl phosphite, and trisbeta-chloroethylphosphite.' 1

However, when chloranil was reacted with phosphites of secondary alcohols, I found that the reaction proceeded on the order of an Arbusov reaction but with the formation of a tetraphosphonate instead of a monophosphonate rather than in accordance with the teachings of Ramirez above in the following manner in, the case of tri-isopropyl phosphite:

vv. o

or or 01 Cl+41 (0 c1111) 0 I (oar-toner P0 0 0.111

+4CsHCl (C|H10)OP POtO CaH'l);

According to this invention, then, there has been discovered new compounds of the following structure:

where R "is a member selected from the group consisting of quinone and hydroquinone and R is a secondary alkyl radical having from 3 to 6 carbon atoms.

' The new compounds of this invention may be prepared by reacting chloranil with a tri-secondary alcohol phosphite preferably in the presence of a suitable solvent. Although the temperature at which the reaction takes place may be varied substantially depending at least in part on the particular phosphite used, temperatures of -425 C. are preferred. Actually the reaction may be conducted'under temperature conditions ranging between 50-150" C. However, when the reaction temperature drops below'50 C. no tetraphosphonate can be detected as a product, Typical of the solvents which may be used are toluene, xylene and dioxane. In general any nonreactive solvent may be-used which has a boiling point higher than the desired reaction temperature. The corresponding tetraphosphonate hydroquinone may be readily formed by hydrogenation with hydrazine or with hydrogen with palladium as a catalyst. However, reduction of the keto groups tovhydroxy groups may be effected by any of the customary methods of reduction. It is to be noted that when a phosphite of a primary alcohol was used in Equation V above, no tetraphosphonate could be isolated or even detected.

The tetraphosphonates of this invention find utility as fuel additives and particularly for inhibiting preignition in gasoline used in internal combustion engines. The hy-' droquinone tetraphosphonates are also useful as a fuel marker due to their fluorescent properties.

The invention is illustrated in greater detail by the following examples:

? isopropyl phosphite (0.26 mole) to a stirred suspension of 24.6 g. chloranil (0.1 mole) in 50 ml. toluene in a suitable reaction container while maintaining the tempe'rature between 105-110? C. After addition of the phosphite the temperature is maintained at 105-110 C. for an additional one-half hour and then cooled 10.75? C. The solvent and any low boiler formed during the reaction are then distilled oil under reduced pressure. At the conclusion of this step the pressure is approximately 20 mm. Hg and the temperature of the reaction vessel is 100 C. By crystallization there is obtained 14.6 g. yellow p-quinone tetrakis (diisopropyl tctraphosphonate). M.P. 154.5155 C.

' product of Example I. The resulting solution is placed with palladium catalyst in a hydrogenation apparatus which is air evacuated and then purged with hydrogen. The hydrogenation is then placed under 60 lbs. of hydrogen for a period of minutes at 35 C. at which the pressure dropped 4 lbs., indicating the acceptance of 0.05 I

The above reduction can also be effected with other.

catalysts such as platinum and nickel.

EXAMPLEIII a. p-Quinone tetrakis (di-secbutyl phosphonate)- By employing the same procedureas set forth in His,- ample I but substituting: 54.9 g. tri-sec. butyl'phosphite (0.219 mole) for the t'r'i-isopropylphosphite, therelis obtained p-quinone' tetrakis (di-sec. butylphosphonate). b. p-Hydroquinone. tetrakis. (di-sec. butyl phosphonate) The product from Example II I(a) aboveis then dissolvedin 500 ml. hexane and 2 g'. hydraz, ine 'are added.

An oily precipitate forms and the" mixture nauseatin thei' with an additional 5 00' mLhexane. The oily material is now separatedand discarded. The remaininghxa ie solution is reduced in volume to 400 r151. by distillation. The solution is then cooled to 70 C. and 5.7 g.,p-hy droquinone tetrakis (di.-sec. butyl phosphonate) precipi tate as pale yellow-green crystals which show. strong fluorescent properties. M.P. 120-121" C.

EXAMPLE p-Quinone tetrakis (di-Z-methyl-penlany1:4-phosph0nate) By employing the sameprocedure as set forth in Ex? ample I but substituting 83.5 (0.25 mole). tri-Z-methylpentanyl-4-phosphite, p-quinone tetrakis (di-2-methyl pentanyl-4-phosphonate) is obtained.

While there have. been. described various embodiments.

of the invention, themethods and compoundsdescribed.

are .not intended to beaunderstoodgas {limiting thelscope' of the invention. as it is realizedthat changes therewithin are possible... Moreover, it is further intendedrthat each element recited in any of the following claims is tob.

understood as referring toall. equivalent elements for accomplishing the same result in substantially the same or equivalent manner, ;it' being intended to cover. the

4 What is claimed is: 1'. Compounds of the structure whereRis asejcondary alkyl havingfrom 3'7to'6 carbon atoms and R is a member selected from the group consisting of quinone and hydroquinone wherein each of the .four ortho and metaepositions-is substitutedwith an alkyl phosphonate radical ofthestructure asshown-enclosed in the above brackets.

2. p-Quinone tetrakis (diisopropyl phosphonate).

3. p-Hydroquinone tetrakis v(di'isopropyl phosphonate).

4. p-Quinone tetrakis (di se c. butyl phosphonate).

5. p-Hydroquinone tetrakis (di-sec. butyl phosphonate).

6, p-Quinone tetrakis (di-Z-methyl-pentanyl-4-phosphonat e).

7'. The method ofpreparing-compounds having the i following structure where R-isa secondary alkyl having from-3 to 6 carbon atoms which comprises reacting a tri-secondary alkyl phosphite with a compound. of .the following structure or I or at a temperature of at least 50 C.

8. Thetmethod of preparingv compounds. having the qllow n s u where R is a secondary alkyl having from 3 to 6 carbon atoms which comprises reacting a tri-secondary alkyl phosphite with a compound of the following structure at a temperature of atleast 50 C. and thereafter hydrogenating said quinone to; the corresponding hydroquinone 9. Themethod; of preparing c'ompoundshaving the following structure invention broadly in whatever formits principles ul ay be utilized. p

where R is a secondary alkyl having from 3 to 6 carbon atoms which comprises reacting a tri-secondary alkyl References Cited in the file of this patent UNITED STATES PATENTS phosphite with chloranil at a temperature of at least 50' 2,553,417 d et 1 May 15, 5 C. to form a quinone tetrakis (di-sec.-arylalkyl tetra- 5 09,376 Ladd et al. Sept. 2, 1952 phosphonate) and thereafter hydrogenating said quinone FOREIGN PATENTS to the corresponding hydroquinone. 503,085 Canada May 25, 1954 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2335,518 May 3, 1 960 Theodor Reetz It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3 line 62,, after "83.5 insert g.

Signed and sealed this 11th day of October 1960.

(s iA Attestzj r KARL H. AXLINE ROBERT C. WATSON Attesting Oflicer Commissioner of Patents 

1. COMPOUNDS OF THE STRUCTURE 